Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Aminolysis of Benzyl 4-Pyridyl Carbonate in Acetonitrile: Effect of Modification of Leaving Group from 2-Pyridyloxide to 4-Pyridyloxide on Reactivity and Reaction Mechanism

  • Bae, Ae-Ri (Department of Chemistry and Nano Science, Ewha Womans University) ;
  • Um, Ik-Hwan (Department of Chemistry and Nano Science, Ewha Womans University)
  • Received : 2012.04.01
  • Accepted : 2012.05.16
  • Published : 2012.08.20
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Abstract

A kinetic study is reported for nucleophilic substitution reactions of benzyl 4-pyridyl carbonate 6 with a series of alicyclic secondary amines in MeCN. The plot of pseudo-first-order rate constant ($k_{obsd}$) vs. [amine] curves upward, which is typical for reactions reported previously to proceed through a stepwise mechanism with two intermediates (i.e., a zwitterionic tetrahedral intermediate $T^{\pm}$ and its deprotonated form $T^-$). Dissection of $k_{obsd}$ into the second- and third-order rate constants (i.e., $Kk_2$ and $Kk_3$, respectively) reveals that $Kk_3$ is significantly larger than $Kk_2$, indicating that the reactions proceed mainly through the deprotonation pathway (i.e., the $k_3$ process) in a high [amine] region. This contrasts to the recent report that the corresponding aminolysis of benzyl 2-pyridyl carbonate 5 proceeds through a forced concerted mechanism. An intramolecular H-bonding interaction was suggested to force the reactions of 5 to proceed through a concerted mechanism, since it could accelerate the rate of leaving-group expulsion (i.e., an increase in $k_2$). However, such H-bonding interaction, which could increase $k_2$, is structurally impossible for the reactions of 6. Thus, presence or absence of an intramolecular H-bonding interaction has been suggested to be responsible for the contrasting reaction mechanisms (i.e., a forced concerted mechanism for the reaction of 5 vs. a stepwise mechanism with $T^{\pm}$ and $T^-$ as intermediates for that of 6).

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References

  1. Castro, E. A. Pure Appl. Chem. 2009, 81, 685-696. https://doi.org/10.1351/PAC-CON-08-08-11
  2. Castro, E. A. Chem. Rev. 1999, 99, 3505-3524. https://doi.org/10.1021/cr990001d
  3. Jencks, W. P. Chem. Rev. 1985, 85, 511-527. https://doi.org/10.1021/cr00070a001
  4. Jencks, W. P. Chem. Soc. Rev. 1981, 10, 345-375. https://doi.org/10.1039/cs9811000345
  5. Jencks, W. P. Acc. Chem. Res. 1980, 13, 161-169. https://doi.org/10.1021/ar50150a001
  6. Menger, F. M.; Smith, J. H. J. Am. Chem. Soc. 1972, 94, 3824- 3829 https://doi.org/10.1021/ja00766a027
  7. Maude, A. B.; Williams, A. J. Chem. Soc., Perkin Trans. 2 1997, 179-183.
  8. Maude, A. B.; Williams, A. J. Chem. Soc., Perkin Trans. 2 1995, 691-696.
  9. Menger, F. M.; Brian, J.; Azov, V. A. Angew. Chem. Int. Ed. 2002, 41, 2581-2584. https://doi.org/10.1002/1521-3773(20020715)41:14<2581::AID-ANIE2581>3.0.CO;2-#
  10. Perreux, L.; Loupy, A.; Delmotte, M. Tetrahedron 2003, 59, 2185-2189. https://doi.org/10.1016/S0040-4020(03)00151-0
  11. Fife, T. H.; Chauffe, L. J. Org. Chem. 2000, 65, 3579-3586. https://doi.org/10.1021/jo9906835
  12. Spillane, W. J.; Brack, C. J. Chem. Soc., Perkin Trans. 2 1998, 2381-2384.
  13. Llinas, A.; Page, M. I. Org. Biomol. Chem. 2004, 2 651-654.
  14. Castro, E. A.; Gazitua, M.; Santos, J. G. J. Phys. Org. Chem. 2011, 24, 466-473. https://doi.org/10.1002/poc.1787
  15. Castro, E. A.; Aliaga, M. E.; Cepeda, M.; Santos, J. G. Int. J. Chem. Kinet. 2011, 43, 353-358. https://doi.org/10.1002/kin.20562
  16. Castro, E. A.; Aliaga, M.; Campodonico, P. R.; Cepeda, M.; Contreras, R.; Santos, J. G. J. Org. Chem. 2009, 74, 9173-9179. https://doi.org/10.1021/jo902005y
  17. Castro, E. A.; Ramos, M.; Santos, J. G. J. Org. Chem. 2009, 74, 6374-6377. https://doi.org/10.1021/jo901137f
  18. Castro, E. A.; Aliaga, M.; Santos, J. G. J. Org. Chem. 2005, 70, 2679-2685. https://doi.org/10.1021/jo047742l
  19. Sung, D. D.; Jang, H. M.; Jung, D. I.; Lee, I. J. Phys. Org. Chem. 2008, 21, 1014-1019. https://doi.org/10.1002/poc.1418
  20. Sung, D. D.; Koo, I. S.; Yang, K.; Lee, I. Chem. Phys. Lett. 2006, 432, 426-430. https://doi.org/10.1016/j.cplett.2006.11.002
  21. Sung, D. D.; Koo, I. S.; Yang, K.; Lee, I. Chem. Phys. Lett. 2006, 426, 280-284. https://doi.org/10.1016/j.cplett.2006.06.015
  22. Oh, H. K.; Oh, J. Y.; Sung, D. D.; Lee, I. J. Org. Chem. 2005, 70, 5624-5629. https://doi.org/10.1021/jo050606b
  23. Oh, H. K.; Jin, Y. C.; Sung, D. D.; Lee, I. Org. Biomol. Chem. 2005, 3, 1240-1244. https://doi.org/10.1039/b500251f
  24. Oh, H. K. Bull. Korean Chem. Soc. 2011, 32, 4095-4098. https://doi.org/10.5012/bkcs.2011.32.11.4095
  25. Oh, H. K. Bull. Korean Chem. Soc. 2011, 32, 1539-1542. https://doi.org/10.5012/bkcs.2011.32.5.1539
  26. Oh, H. K. Bull. Korean Chem. Soc. 2011, 32, 137-140. https://doi.org/10.5012/bkcs.2011.32.1.137
  27. Oh, H. K.; Ku, M. H.; Lee, H. W.; Lee, I. J. Org. Chem. 2002, 67, 8995-8998/ https://doi.org/10.1021/jo0264269
  28. Oh, H. K.; Ku, M. H.; Lee, H. W.; Lee, I. J. Org. Chem. 2002, 67, 3874-3877. https://doi.org/10.1021/jo025637a
  29. Um, I. H.; Lee, J. Y.; Ko, S. H.; Bae, S. K. J. Org. Chem. 2006, 71, 5800-5803. https://doi.org/10.1021/jo0606958
  30. Um, I. H.; Kim, K. H.; Park, H. R.; Fujio, M.; Tsuno, Y. J. Org. Chem. 2004, 69, 3937-3942. https://doi.org/10.1021/jo049694a
  31. Um, I. H.; Min, J. S.; Ahn, J. A.; Hahn, H. J. J. Org. Chem. 2000, 65, 5659-5663. https://doi.org/10.1021/jo000482x
  32. Um, I. H.; Jeon, S. E.; Seok, J. A. Chem. Eur. J. 2006, 12, 1237- 1243. https://doi.org/10.1002/chem.200500647
  33. Um, I. H.; Seok, J. A.; Kim, H. T.; Bae, S. K. J. Org. Chem. 2003, 68, 7742-7746. https://doi.org/10.1021/jo034637n
  34. Um, I. H.; Hwang, S. J.; Baek, M. H.; Park, E. J. J. Org. Chem. 2006, 71, 9191-9197. https://doi.org/10.1021/jo061682x
  35. Um, I. H.; Han, J. Y.; Shin, Y. H. J. Org. Chem. 2009, 74, 3073-3078. https://doi.org/10.1021/jo900219t
  36. Um, I. H.; Akhtar, K.; Shin, Y. H.; Han, J. Y. J. Org. Chem. 2007, 72, 3823-3829. https://doi.org/10.1021/jo070171n
  37. Um, I. H.; Shin, Y. H.; Han, J. Y.; Mishima, M. J. Org. Chem. 2006, 71, 7715-7720. https://doi.org/10.1021/jo061308x
  38. Bae, A. R.; Um, I. H. Bull. Korean Chem. Soc. 2012. 33, in press.
  39. Um, I. H.; Kang, J. S.; Kim, C. W.; Lee, J. I. Bull. Korean Chem. Soc. 2012, 33, in press.
  40. Lee, J. I.; Kang, J. S.; Kim, S. I.; Um, I. H. Bull. Korean Chem. Soc. 2010, 31, 2929-2933. https://doi.org/10.5012/bkcs.2010.31.10.2929
  41. Lee, J. I.; Kang, J. S.; Im, L. R.; Um, I. H. Bull. Korean Chem. Soc. 2010, 31, 3543-3548. https://doi.org/10.5012/bkcs.2010.31.12.3543
  42. Lee, J. I. Bull. Korean Chem. Soc. 2010, 31, 749-752. https://doi.org/10.5012/bkcs.2010.31.03.749
  43. Lee, J. I. Bull. Korean Chem. Soc. 2007, 28, 863-866. https://doi.org/10.5012/bkcs.2007.28.5.863
  44. Lee, J. I.; Kim, S. Bull. Korean Chem. Soc. 1989, 10, 611-612.
  45. Kim, S.; Lee, J. I. J. Org. Chem. 1984, 49, 1712-1716. https://doi.org/10.1021/jo00184a009
  46. Kim, S.; Lee, J. I. Tetrahedron Lett. 1984, 25, 4943-4946. https://doi.org/10.1016/S0040-4039(01)91265-1
  47. Kim, S.; Lee, J. I. J. Org. Chem. 1983, 48, 2608-2610. https://doi.org/10.1021/jo00163a040
  48. Mukaiyama, T.; Araki, M.; Takei, H. J. Am. Chem. Soc. 1973, 95, 4763-4765. https://doi.org/10.1021/ja00795a055
  49. Araki, M.; Sakata, S.; Takei, H.; Mukaiyama, T. Bull. Chem. Soc. Jpn. 1974, 47, 1777-1780. https://doi.org/10.1246/bcsj.47.1777
  50. Kang, J. S.; Lee, J. I.; Um, I. H. Bull. Korean Chem. Soc. 2012. 33, in press.
  51. Castro, E. A.; Ibanez, F.; Santos, J. G.; Ureta, C. J. Org. Chem. 1993, 58, 4908-4912. https://doi.org/10.1021/jo00070a028
  52. Castro, E. A.; Galvez, A.; Leandro, L.; Santos, J. G. J. Org. Chem. 2002, 67, 4309-4315. https://doi.org/10.1021/jo025562a
  53. Castro, E. A.; Cubillos, M.; Santos, J. G. J. Org. Chem. 2001, 66, 6000-6003. https://doi.org/10.1021/jo0100695
  54. Castro, E. A.; Garcia, P.; Leandro, L.; Quesieh, N.; Rebolledo, A. Santos, J. G. J. Org. Chem. 2000, 65, 9047-9053. https://doi.org/10.1021/jo005587e
  55. Oh, H. K.; Kim, S. K.; Lee, H. W.; Lee, I. J. Chem. Soc., Perkin Trans. 2 2001, 1753-1757.
  56. Oh, H. K.; Kim, S. K.; Lee, H. W.; Lee, I. New J. Chem. 2001, 25, 313-317. https://doi.org/10.1039/b006974o
  57. Oh, H. K.; Kim, S. K.; Cho, I. H.; Lee, H. W.; Lee, I. New J. Chem. 2001, 25,
  58. Oh, H. K.; Kim, S. K.; Cho, I. H.; Lee, H. W.; Lee, I. Chem. Soc., Perkin Trans. 2 2000, 2306-2310
  59. Oh, H. K.; Woo, S. Y.; Shin, C. H.; Park, Y. S.; Lee, I. J. Org. Chem. 1997, 62, 5780-5784. https://doi.org/10.1021/jo970413r
  60. Spillane, W. J.; McGrath, P.; Brack, C.; O'Byrne, A. B. J. Org. Chem. 2001, 66, 6313-6316. https://doi.org/10.1021/jo015691b
  61. Kim, S. I.; Baek, H. W.; Um, I. H. Bull. Korean Chem. Soc. 2009, 30, 2909-2912. https://doi.org/10.5012/bkcs.2009.30.12.2909
  62. Bell, R. P. The Proton in Chemistry; Methuen: London, 1959; p 159.
  63. Jencks, W. P.; Regenstein, F. In Handbook of Biochemistry, Selected Data for Molecular Biology; Sober, H. A., Ed.; The Chemical Rubber Co.: Cleveland, OH, 1968.
  64. Kim, S.; Lee, J. I. Chem. Lett. 1984, 237-238.
  65. Kim, S.; Lee, J. I.; Yi, K. Y. Bull. Chem. Soc. Jpn. 1985, 58, 3570-3575. https://doi.org/10.1246/bcsj.58.3570

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